Hofmann-Martius rearrangement
- Hofmann-Martius rearrangement
The Hofmann-Martius rearrangement in organic chemistry is a rearrangement reaction converting an N-alkylated aniline to the corresponding ortho and / or para aryl-alkylated aniline. The reaction requires heat and the catalyst is an acid like hydrochloric acid [Hofmann, A. W.; Martius, C. A. Ber 1871 4, 742-748.] [Hofmann, A. W. Ber 1872, 5, 720-722.]
:
When the catalyst is a metal halide the reaction is also called the Reilly-Hickinbottom rearrangement [Reilly, J.; Hickinbottom, W. J. J. Chem.Soc. 1920, 103-137] .
The reaction is also known to work for aryl ethers and two conceptually related reactions are the Fries rearrangement and the Fischer-Hepp rearrangement. Its reaction mechanism centers around dissociation of the reactant with the positively charged organic residue R attacking the aniline ring in a Friedel-Crafts alkylation.
In one study this rearrangement is applied to a "3-N(CH3)(C6H5)-2-oxindole" ["Thermal and Acid-Catalyzed Hofmann-Martius Rearrangement of 3-N-Aryl-2-oxindoles into 3-(Arylamino)-2-oxindoles" Philip Magnus and Rachel Turnbull Org. Lett.; 2006; 8(16) pp 3497 - 3499; (Letter) DOI|10.1021/ol061191z] [heating 1 in toluene at 80°C gives 30% 2-o (ortho) and 37% 2-p (para)] :
:
References
Wikimedia Foundation.
2010.
Look at other dictionaries:
Martius — may refer to: an adjectival form of the theonym Mars in Latin: Campus Martius, the Field of Mars in ancient Rome Martius, the month of March; see Roman calendar Telo Martius, an ancient name for Toulon, France People named Martius: Carl Friedrich … Wikipedia
Wallach rearrangement — The Wallach rearrangement, named after Otto Wallach, is an organic reaction and a rearrangement reaction converting an aromatic azoxy compound with sulfuric acid to an azo compound with one arene ring substituted by an hydroxyl group in the… … Wikipedia
Fries rearrangement — The Fries rearrangement, named for the German chemist Karl Theophil Fries, is a rearrangement reaction of a phenyl ester to a hydroxy aryl ketone by catalysis of lewis acids. [cite journal title = Über Homologe des Cumaranons und ihre Abkömmlinge … Wikipedia
Bamberger rearrangement — The Bamberger rearrangement is the chemical reaction of N phenylhydroxylamines with strong aqueous acid, which will rearrange to give 4 aminophenols.cite journal | last = Bamberger | first = E. | journal = Chem. Ber. | date = 1894 | volume = 27 | … Wikipedia
List of organic reactions — Well known reactions and reagents in organic chemistry include Contents: A B C D E F G H I J K L M N O P Q R S T U V W X Y Z See also Ext … Wikipedia
Amine — For other uses, see Amine (disambiguation). Primary amine Secondary amine Tertiary amine … Wikipedia
Transposición de Bamberger — La Transposición de Bamberger es una reacción orgánica en donde se hace reaccionar N fenilhidroxilaminas con un ácido fuerte en medio acuoso; cuando la transposición se lleva a cabo la transposición se obtienen 4 aminofenoles.[1] [2] Fue descrita … Wikipedia Español